US5679180A - γ strengthened single crystal turbine blade alloy for hydrogen fueled propulsion systems - Google Patents

γ strengthened single crystal turbine blade alloy for hydrogen fueled propulsion systems Download PDF

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Publication number
US5679180A
US5679180A US08/493,610 US49361095A US5679180A US 5679180 A US5679180 A US 5679180A US 49361095 A US49361095 A US 49361095A US 5679180 A US5679180 A US 5679180A
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alloy
hydrogen
nickel
single crystal
strengthened
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US08/493,610
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English (en)
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Daniel P. DeLuca
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RPW ACQUISITION LLC
Aerojet Rocketdyne Inc
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United Technologies Corp
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Assigned to UNITED TECHNOLOGIES CORPORATION reassignment UNITED TECHNOLOGIES CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DELUCA, DANIEL P.
Priority to GB9612123A priority patent/GB2302550B/en
Priority to DE19623943A priority patent/DE19623943C2/de
Priority to FR9607531A priority patent/FR2735792B1/fr
Priority to JP16154696A priority patent/JP3525402B2/ja
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Assigned to WELLS FARGO BANK, NATIONAL ASSOCIATION reassignment WELLS FARGO BANK, NATIONAL ASSOCIATION SECURITY AGREEMENT Assignors: AEROJET-GENERAL CORPORATION
Assigned to U.S. BANK NATIONAL ASSOCIATION reassignment U.S. BANK NATIONAL ASSOCIATION SECURITY AGREEMENT Assignors: AEROJET-GENERAL CORPORATION
Assigned to AEROJET ROCKETDYNE, INC. reassignment AEROJET ROCKETDYNE, INC. MERGER/CHANGE OF NAME Assignors: RPW ACQUISITION LLC
Assigned to RPW ACQUISITION LLC reassignment RPW ACQUISITION LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: UNITED TECHNOLOGIES CORPORATION
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Assigned to AEROJET ROCKETDYNE, INC. (F/K/A AEROJET-GENERAL CORPORATION) reassignment AEROJET ROCKETDYNE, INC. (F/K/A AEROJET-GENERAL CORPORATION) RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: U.S. BANK NATIONAL ASSOCIATION
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/52—Alloys

Definitions

  • the present invention relates to a ⁇ " strengthened nickel-based alloy having an improved resistance to hydrogen embrittlement and to a process for forming such an alloy.
  • Precipitation strengthened (by ⁇ ' and/or ⁇ ") nickel base alloys have been the material of choice in many aerospace applications such as high stress, high temperature gas turbine applications. In turbine blade and vane applications, ⁇ ' alloys are cast in single crystal form.
  • Nickel base superalloys are also the materials of choice for liquid hydrogen fueled rocket engine turbopumps. They are used extensively in current versions of the NASA Space Shuttle Main Engine. When used in this environment, the nickel based alloys encounter hydrogen embrittlement.
  • Cast ⁇ ' strengthened alloys such as single crystal PWA 1480 and equiaxed MAR-M-247 are used in turbopump hot section applications where temperatures approach 900° C.
  • Columnar grain directionally solidified (DS) castings or single crystal forms are preferred for turbine blades and are exclusively of the ⁇ ' type.
  • Equiaxed (EQ) castings again of the ⁇ ' type are used in vane applications.
  • the ⁇ ' strengthening precipitate in these alloys is composed of alloyed Ni 3 Al with L1 2 order. It assumes a cuboidal morphology geometrically ordered in the ⁇ matrix. The cube edges are aligned with the ⁇ 001> directions.
  • ⁇ " precipitation strengthened alloys such as INCO 718 find use in many structural applications such as pump housings and flanges. Their service temperature is generally limited to 650° C. They are used exclusively in equiaxed form, wrought or cast. The primary strengthening precipitate in these alloys is ⁇ " (ordered Ni 3 Cb) and assumes a lenticular morphology. ⁇ " precipitates exhibit both atomic (DO 22 ) and geometric order, coherent with the ⁇ 001> directions. They are much finer than those found in cast ⁇ ' strengthened alloys and of a lower volume fraction.
  • Decohesion has been shown to be sub microscopic (111) fracture confined to the ⁇ matrix phase. The result is a separation at the ⁇ - ⁇ ' interface.
  • the normal fracture mode observed in air is by shearing of ⁇ ' precipitates on (111) planes.
  • the ⁇ " alloy, PWA 1490, used in the studies also experienced the transition to intergranular fracture in the presence of hydrogen but did not show a tendency to fail by matrix/precipitate decohesion.
  • the results of the study demonstrated that ⁇ " strengthened alloys possess an intrinsic immunity to hydrogen induced matrix precipitate decohesion.
  • a nickel base alloy having an improved resistance to hydrogen embrittlement is a ⁇ " strengthened single crystal nickel base alloy containing from about 11 to 13 wt % chromium, from about 17 to 19 wt % iron, from about 2.8 to 3.3 wt % molybdenum, from about 1.75 to about 2.25 wt % titanium, from about 8.75 to about 6.25 wt % columbium and tantalum, from about 0.40 to about 0.80 wt % aluminum, from about 0.02 to about 0.06 carbon and the balance primarily nickel.
  • the ⁇ " strengthened nickel base alloy consists essentially of from about 0.02 to about 0.06 wt % carbon, up to about 0.35 wt % manganese, up to about 0.15 wt % silicon, up to about 0.015 wt % phosphorous, up to about 0.005 wt % sulfur, from about 11 to 13 wt % chromium, from about 17 to 19 wt % iron, up to about 1.0 wt % cobalt, from about 2.80 to 3.30 wt % molybdenum, from about 5.75 to 6.25 wt % columbium+tantalum, from about 1.75 to 2.25 wt % titanium, from about 0.4 to 0.8 wt % aluminum, up to about 0.005 wt % boron, up to about 0.10 wt % copper, up to about 0.03 wt % zirconium, up to about 5 ppm lead, up to about 0.3 ppm bis
  • the ⁇ " strengthened nickel based alloy of the present invention may be formed by providing a nickel base alloy as above in molten form, casting the nickel base alloy in single crystal form, and thereafter subjecting it to a two step heat treatment.
  • the cast alloy is homogenized at a temperature in the range of from about 1200° C. to about 1250° C., preferably from about 1215° C. to about 1235° C., for a time period in the range of 3.75 to 4.25 hours.
  • the homogenized cast alloy is cooled to room temperature and subjected to a second precipitation hardening heat treatment.
  • the precipitation hardening heat treatment is carried out at a temperature in the range of from about 750° C. to about 800° C., preferable from about 750° C. to about 770° C., for a time in the range of from about 7.75 to about 8.25 hours.
  • the present invention relates to a ⁇ " strengthened nickel base alloy have improved resistance to hydrogen embrittlement.
  • the improved nickel base alloy in accordance with the present invention contains from about 11 to 13 wt % chromium, from about 17 to 19 wt % iron, from about 2.8 to about 3.3 wt % molybdenum, from about 1.75 to about 2.25 wt % titanium, from about 5.75 to 6.25 wt % columbium and tantalum, from about 0.02 to 0.06 wt % carbon, from about 0.40 to 0.80 wt % aluminum/, and the balance primarily nickel.
  • the nickel base alloy of the present invention consists essentially of from about 0.02 to about 0.06 wt % carbon, up to about 0.35 wt % manganese, up to about 0.15 wt % silicon, up to about 0.015 wt % phosphorous, up to about 0.005 wt % sulfur, from about 11 to 13 wt % chromium, from about 17 to 19 wt % iron, up to about 1.0 wt % cobalt, from about 2.8 to 3.3 wt % molybdenum, from about 5.75 to 6.25 wt % columbium+tantalum, from about 1.75 to 2.25 wt % titanium, from about 0.4 to 0.8 wt % aluminum, up to about 0.005 wt % boron, up to about 0.1 wt % copper, up to about 0.03 wt % zirconium, up to about 5 ppm lead, up to about 0.3 ppm bis
  • the nickel base alloy of the present invention must be cast as a single crystal so as to provide the desired resistance to hydrogen embrittlement.
  • the formation of the alloy into single crystal form is a critical aspect of the present invention, but the method of single crystal formation is unimportant.
  • One method which can be used is described in U.S. Pat. No. 3,494,709, which is hereby incorporated by reference.
  • Another method which can be used consists of pouring superheated metal into a ceramic mold under high vacuum conditions and withdrawing heat from the lower portion of the mold which is seated on a water-cooled copper chill. Grains are nucleated on the chill surface and grow in a columnar manner parallel to a unidirectional temperature gradient. At the water-cooled copper chill, many grains are nucleated with essentially random orientations. However, the ⁇ 001> growth rate is higher than others. As solidification proceeds, the grains enter a helical single crystal selector. After one or two turns of the helix, only one crystal survives and this grain fills the entire mold cavity.
  • the material is subjected to a homogenization treatment.
  • the homogenization treatment is carried out at a temperature in the range of from about 1200° C. to about 1250° C., preferably from about 1215° C. to about 1235° C., for a time in the range of from about 3.75 to about 4.25 hours.
  • the homogenization treatment may be carried out using any suitable heat treatment device known in the art and using any suitable protective atmosphere. During this homogenization treatment, all phases precipitated during solidification are put into solution.
  • the material After homogenization, the material is cooled to room temperature. This can be done using fan cooling. Thereafter, the material is subjected to a precipitation hardening treatment.
  • the precipitation hardening treatment is carried out at a temperature in the range of from about 750° C. to about 800° C., preferably from about 750° C. to about 770° C., for a time in the range of from about 7.75 hours to about 8.25 hours.
  • the precipitation hardening treatment may be carried out using any suitable heat treatment device known in the art and using any suitable protective atmosphere. This treatment is intended to precipitate a high volume fraction of fine ⁇ " precipitates.
  • One method of expressing the susceptibility of a particular material to hydrogen degradation relative to that of another material is to determine each material's hydrogen to air debit for some mechanical property known to be degraded by exposure to hydrogen.
  • the following example was performed.
  • a mold of cast test bars of a nickel base alloy having a nominal composition of 12 wt % chromium, 18 wt % iron, 2.0 wt % titanium, 0.60 wt % aluminum, 3.05 wt % molybdenum, 6.0 wt % columbium+tantalum, 0.04 wt % carbon and the balance nickel was produced in single crystal form.
  • the bars were 0.5 cm in diameter and approximately 10 cm. long.
  • the material was homogenized at 1225° C. for four hours followed by a fan cool to room temperature. Thereafter, a precipitation treatment was carried out at 760° C. for eight hours.
  • Notched low cycle fatigue test specimens were machined from the cast bars. Low cycle fatigue tests were conducted at 26° C. with a stress ratio of 0.05 at 0.17 Hz. Cylindrical gage notched low cycle fatigue specimens were tested at a net section stress of 620.5 MPa in air and 34.5 MPa in gaseous hydrogen. Fatigue life (cycles to failure) was determined in air and hydrogen and the ratio of air to hydrogen fatigue life was determined.
  • the notched low cycle fatigue life for the single crystal nickel base alloy made in accordance with the present invention in hydrogen was greater than that of PWA 1480, a ⁇ ' strengthened turbine blade alloy used in advanced NASA Space Shuttle Main Engine turbopump designs, in hydrogen and the air to hydrogen life ratio was found to be only 5X, significantly lower than the 100X ratio observed for PWA 1480,
  • ⁇ " strengthened single crystal nickel based alloys formed in accordance with the present invention can be used to manufacture components for hydrogen fueled rocket engine components such as turbopumps.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
US08/493,610 1995-06-22 1995-06-22 γ strengthened single crystal turbine blade alloy for hydrogen fueled propulsion systems Expired - Lifetime US5679180A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US08/493,610 US5679180A (en) 1995-06-22 1995-06-22 γ strengthened single crystal turbine blade alloy for hydrogen fueled propulsion systems
GB9612123A GB2302550B (en) 1995-06-22 1996-06-10 Strengthened single crystal turbine blade alloy for hydrogen fueled propulsion systems
DE19623943A DE19623943C2 (de) 1995-06-22 1996-06-15 gamma-gehärtete einkristalline Turbinenschaufellegierung für mit Wasserstoff betriebene Triebwerkssysteme, Formgegenstand und wärmebehandelter Gegenstand daruas sowie Verfahren zur Herstellung der Legierung
FR9607531A FR2735792B1 (fr) 1995-06-22 1996-06-18 Alliage monocristallin renforce par gamma" pour aube de turbine de systemes de propulsion utilisant de l'hydrogene
JP16154696A JP3525402B2 (ja) 1995-06-22 1996-06-21 ニッケルをベースとする合金の製造方法

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Application Number Priority Date Filing Date Title
US08/493,610 US5679180A (en) 1995-06-22 1995-06-22 γ strengthened single crystal turbine blade alloy for hydrogen fueled propulsion systems

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US5679180A true US5679180A (en) 1997-10-21

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JP (1) JP3525402B2 (de)
DE (1) DE19623943C2 (de)
FR (1) FR2735792B1 (de)
GB (1) GB2302550B (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030034098A1 (en) * 2001-04-24 2003-02-20 General Electric Company Nickel-base superalloys and articles formed therefrom
US20050120941A1 (en) * 2003-12-04 2005-06-09 Yiping Hu Methods for repair of single crystal superalloys by laser welding and products thereof
US20100269887A1 (en) * 2007-08-31 2010-10-28 Arcelormittal-Stainless And Nickel Alloys Crystallographically textured metal substrate, crystallographically textured device, cell and photovoltaic module including such device and thin layer deposition method

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Publication number Priority date Publication date Assignee Title
US20030034098A1 (en) * 2001-04-24 2003-02-20 General Electric Company Nickel-base superalloys and articles formed therefrom
US6531002B1 (en) * 2001-04-24 2003-03-11 General Electric Company Nickel-base superalloys and articles formed therefrom
USRE40501E1 (en) * 2001-04-24 2008-09-16 General Electric Company Nickel-base superalloys and articles formed therefrom
US20050120941A1 (en) * 2003-12-04 2005-06-09 Yiping Hu Methods for repair of single crystal superalloys by laser welding and products thereof
US20100269887A1 (en) * 2007-08-31 2010-10-28 Arcelormittal-Stainless And Nickel Alloys Crystallographically textured metal substrate, crystallographically textured device, cell and photovoltaic module including such device and thin layer deposition method
KR101537305B1 (ko) * 2007-08-31 2015-07-22 아뻬람 알로이스 엥피 결정학적 집합조직의 금속 기판, 결정학적 집합조직의 디바이스, 전지 및 그러한 디바이스를 포함하는 광전지 모듈과, 박층 퇴적 방법
US9309592B2 (en) * 2007-08-31 2016-04-12 Arcelormittal-Stainless And Nickel Alloys Crystallographically textured metal substrate, crystallographically textured device, cell and photovoltaic module including such device and thin layer deposition method

Also Published As

Publication number Publication date
GB2302550B (en) 1998-07-08
JPH09157811A (ja) 1997-06-17
GB9612123D0 (en) 1996-08-14
DE19623943C2 (de) 2002-02-07
DE19623943A1 (de) 1997-01-02
GB2302550A (en) 1997-01-22
FR2735792A1 (fr) 1996-12-27
JP3525402B2 (ja) 2004-05-10
FR2735792B1 (fr) 1999-05-07

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